Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing

ABSTRACT

A slick water fracturing fluid including a brine, an inorganic nitrate, a nitrogen reducing bacteria, a scale inhibitor selected from the group consisting of a polyacrylate polymer, a polyacrylate copolymer, a polyacrylate terpolymer, and mixtures thereof, and a friction reducer, wherein the friction reducer is a polyacrylamide.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and is a divisional application ofU.S. patent application Ser. No. 14/755,186, filed Jun. 30, 2015, andentitled “METHOD FOR THE USE OF NITRATES AND NITRATE REDUCING BACTERIAIN HYDRAULIC FRACTURING,” which is a divisional application of U.S.patent application Ser. No. 13/213,781, filed Aug. 19, 2011, andentitled “METHOD FOR THE USE OF NITRATES AND NITRATE REDUCING BACTERIAIN HYDRAULIC FRACTURING,” the entire disclosures of which areincorporated herein by reference; and to U.S. Provisional Application61/385,011, filed Sep. 21, 2010, and entitled “METHOD FOR THE USE OFNITRATES AND NITRATE REDUCING BACTERIA IN HYDRAULIC FRACTURING”.

BACKGROUND OF THE DISCLOSURE

The present disclosure relates generally to the field of fracturingfluids used in fracturing subterranean formations during hydrocarbonrecovery. More specifically the present disclosure relates to methodsfor introducing additives in fracturing fluids to supplement or replacetraditional biocides.

Hydraulic fracturing is a formation stimulation technique used to createadditional permeability in a producing formation to increase the flow ofhydrocarbons toward the wellbore. Typically, during a hydraulicfracturing operation, a high hydraulic pressure is used to fracture thesubterranean formation, creating cracks that facilitate the increasedflow of hydrocarbons. Often, proppants are used to keep cracks open thatare created during the fracturing operation.

Fracturing fluids include a number of components and are most oftenwater-based. These components typically include acids, biocides,breakers, corrosion inhibitors, friction reducers, gels, iron controlchemicals, oxygen scavengers, surfactants and scale inhibitors.Fracturing fluids that contain friction reducers to allow higher flowrates are most often termed “slick water” fracturing fluids.

In most traditional hydraulic fracturing operations, much of thefracturing fluid used is recovered. However, in certain formations andoperations, the majority of the fracturing fluid that enters thesubterranean formation is not initially recovered, but, instead, remainsin the formation. This is particularly true for small pore-sized, lowpermeability formations such as gas-producing shale formations. Someshales may have unfractured permeabilities of 0.01 to 0.00001millidarcies. Effective porosity of shales may be 0.2% or less. As aresult, it may be possible to initially recover only 15% or less of thefracturing fluid, with the rest of the fracturing fluid remaining insitu.

The unrecovered fracturing fluid in the formation may provide a fertilebreeding ground for the anaerobic bacteria present in thehydrocarbon-producing formation. Certain types of bacteria, for example,sulfate reducing bacteria (SRB), can be detrimental to both the recoveryof the hydrocarbon and the hydrocarbon itself. SRB act to reducesulfates to sulfides which are detrimental to both the formation itself,as well as to the hydrocarbon recovered. For instance, the SRB maycreate sludge or slime, which can reduce the porosity of the formationand thereby impede hydrocarbon recovery. SRB may also produce hydrogensulfide which may sour the hydrocarbon, as well as cause corrosion inmetal tubulars and surface equipment.

Typical fracturing fluids include a biocide in order to control of theaction of bacteria such as SRB. However, some of these biocides, suchas, for instance, glutaraldehye, present environmental issues. Groundwater may be contaminated with the biocide, for instance, duringfracturing operations, or through spills of fracturing fluids at thesurface. Further, more reactive biocides such as oxidizers tend to havea limited life in the formation. This limited life may present a seriousproblem in low porosity, low permeability formations, where fracturingfluids may remain for a significant period of time due to low mobility.

Other problems exist with traditional fracturing fluids whereenvironmentally sensitivity is an issue. For instance, certain frictionreducers and scale inhibitors may be toxic.

What is needed is a method of controlling undesirable bacteria, such asSRB, in small pore-sized, low permeability formations without the use oftraditional biocides during hydraulic fracturing operations. Further,what is needed is a fracturing fluid with less toxic components thantraditional fracturing fluids.

SUMMARY OF THE DISCLOSURE

The compounds and methods described herein relate generally to the fieldof gas and oil production. Other uses may also be made of same. Inparticular, compositions and methods for controlling the growth ofsulfate reducing bacteria are described.

In one embodiment of the present disclosure, a method of controllingsulfides in a low porosity, low permeability subterranean formation isdisclosed which includes injecting an inorganic nitrate into theformation.

In another embodiment of the present disclosure, a slick waterfracturing fluid is disclosed which includes, a brine, an inorganicnitrate, a nitrogen reducing bacteria, a scale inhibitor. The scaleinhibitor is a polyacrylate polymer, a polyacrylate copolymer, apolyacrylate terpolymer, or mixtures thereof. The slick water fracturingfluid further includes a friction reducer that is a polyacrylamide.

DETAILED DESCRIPTION

In the present disclosure, inorganic nitrates or inorganic nitrites areinjected with the fracturing fluid to stimulate nitrate-reducingbacteria or nitrate reducing sulfide oxidizing bacteria (NRSOB)(generically, “NRB”) as a control mechanism for SRB in place of atraditional biocide in a low porosity, low permeability subterraneanformation, such as shale. Molybdates also may be used in conjunctionwith the inorganic nitrates as a control mechanism for SRB.

SRB and NRB typically compete for the same non-polymer carbon source(such as acetates) present in the subterranean formation needed forgro′″1:h of bacteria. By increasing the growth rate of the NRB incomparison to the SRB, the NRB may out compete the SRB in consumption ofthe available non-polymer carbon source, depriving the SRB of itsability to grow and create the undesirable sulfides. Further, byinhibiting the growth rate of the SRB, the NRB may predominate, againout competing the SRB for the available non-polymer carbon in thesubterranean formation.

Often, in low permeability, low porosity formations such as shales,recovery of the fracturing fluid is limited due to limited mobility; asa result, a significant portion of the fracturing fluid may remain inthe formation for weeks and even months. Short acting biocides typicallyused to control the growth of SRB are often ineffective in suchapplications, as their efficacy may be limited to mere hours or days,allowing SRB growth following the initial biocide use. Other traditionalpersistent biocides may represent a health risk, in that spills ormigration into groundwater may create an undesirable hazard. Incontrast, the mechanism of the current disclosure may increase inefficacy with time, as the NRB out compete the SRB with time, and, withrespect to NRSOB, may serve to mediate damage done by SRB. Further, theNRB does not pose the health or environmental risks related to thetraditional biocides.

Inorganic nitrates serve to stimulate the growth of the NRB present inthe subterranean formation or the water that serves as a basis for thefracturing fluid, thus outcompeting SRB present in the formation.Inorganic nitrates may be used as part of the fracturing fluid injectedinto the subterranean formation. Inorganic nitrates available for use inthe present disclosure include, for instance, potassium nitrate, sodiumnitrate, ammonium nitrate, and mixtures thereof. These inorganicnitrates are commonly available, but are non-limiting and anyappropriate inorganic nitrate may be used.

The amount of inorganic nitrate included as part of the fracturing fluidis dependent upon a number of factors, including the amount of sulfatein the hydrocarbon, the amount of sulfate in the fracturing fluiditself, the permeability of the formation, and the expected amount ofNRB needed to counteract the SRB. Typical concentration of inorganicnitrate in the fracturing fluid is less than 2000 ppm by weight of thesolution. More often, the concentration of inorganic nitrate is between500 to 1000 ppm by weight, most often between about 700 and 800 ppm byweight.

NRB are often indigenous in the subterranean formation or alreadypresent in the fracturing fluid and simple addition of the inorganicnitrate may be adequate to stimulate the NRB to outcompete SRB for thenon-polymer carbon source. However, in certain circumstances, such aswhen the indigenous amount of NRB is inadequate or wholly absent, it maybe necessary to supplement the indigenous NRB with suitable additionalNRB in the fracturing fluid. Thus, in certain embodiments of the presentdisclosure, NRB are added to the fracturing fluid.

Those of ordinary skill in the art with the benefit of this disclosurewill recognize acceptable examples of NRB appropriate for use in thisdisclosure. NRB include any type of microorganism capable of performinganaerobic nitrate reduction, such as heterotrophic nitrate-reducingbacteria, and nitrate-reducing sulfide-oxidizing bacteria. This mayinclude, but is not limited to, Campylobacter sp. Nitrobacter sp.,Thiobacillus sp., Nitrosomonas sp., Thiomicrospira sp., Sulfurospirillumsp., Thauera sp., Paracoccus sp., Pseudomonas sp., Rhodobacter sp., orSpecific examples include, but are not limited to, Nitrobacter vulgaris,Nitrosomonas europea, Pseudomonas stutzeri, Pseudomonas aeruginosa,Paracoccus denitrificans, Sulfurospirillum deleyianum, and Rhodobactersphaeroides.

The amount of NRB included in the fracturing fluid will depend upon anumber of factors including the amount of SRB expected, as well as thepermeability and porosity of the subterranean formation. In certainembodiments of the present disclosure, the amount of NRB in thefracturing fluid is between 1 and 10⁸ bacteria count/ml of thefracturing fluid, preferably between 10¹ and 10⁴ bacteria count/ml ofthe fracturing fluid.

NRB of the present disclosure may convert inorganic nitrates tonitrites. In addition, in certain embodiments of the present disclosure,the NRB of the present disclosure also may convert nitrites to ammonia.In certain other embodiments of the present disclosure, the NRB of thepresent disclosure may convert ammonia to nitrogen gas. Thus, inaddition to adding nitrates to the fracturing fluid, in certainembodiments of the present disclosure, inorganic nitrites may also beadded to the fracturing fluid. It has further been found that nitritesmay scavenge hydrogen sulfide, further reducing the souring of thehydrocarbon produced. Inorganic nitrites include, for instance sodiumnitrite and potassium nitrite and are typically added in the range ofbetween about 5 and 100 ppm by weight of the fracturing fluid.

In addition to stimulating the NRB to out compete the SRB, it may bedesirable to introduce additional SRB inhibitors in certain embodimentsof the present disclosure together with the inorganic nitrates. Examplesof SRB inhibitors suitable for the present disclosure are9,10-anthraquinone, molybdates and molybdate salts, such as sodiummolybdate and lithium molybdate, although any SRB inhibitor may be usedin concentrations where the molybdates do not unduly affect the abilityof the NRB to otherwise out compete the SRB. In certain embodiments ofthe present disclosure, molybdate is added to the fracturing fluid inthe range of 5 to about 100 ppm by weight of fluid.

Thus, as described in the present disclosure, less effective and lessenvironmentally-sensitive biocides may be replaced with long-actingalternatives, particularly in low porosity, low permeability formations,such as shale. In addition, it may be advantageous, particularly inenvironmentally sensitive situations, such as where possibility ofground water contamination exists, to substitute other toxic componentsof traditional slick water fracturing fluids with less toxicalternatives.

For example, traditional fracturing fluids use scale inhibitors toreduce scale buildup in the formation or production equipment that mayprecipitate from the brine used as a base for the fracturing fluid. Incertain embodiments of the present disclosure, polyacrylate polymers,copolymers, and terpolymers have been found to be compatible withnitrates and NRBs, effective and present few, if any, environmentalissues.

As another example, slick water hydraulic fracturing fluids includefriction reducers. Latex polymers and copolymers of polyacrylamides havebeen found to be compatible with nitrates and NRBs, effective, andpresent, few if any, environmental issues.

This disclosure will now be further illustrated with respect to certainspecific examples which are not intended to limit the disclosure, butrather to provide more specific embodiments as only a few of manypossible embodiments.

Example 1

A fracturing fluid may be prepared with sufficient sodium nitrate tobring the sodium nitrate concentration in the fracturing fluid to about800 ppm by weight. The fracturing fluid may then be injected into ahydrocarbon-producing, subterranean shale formation.

Example 2

A fracturing fluid may be prepared in accordance with Example 1.Sulfurospirillum deleyianum may be added to the fracturing fluid insufficient amounts to bring the concentration of the NRB to about 10²bacteria count/ml fracturing fluid. The fracturing fluid may then beinjected as in Example 1.

Example 3

A fracturing fluid may be prepared in accordance with Example 1. Sodiummolybdate may be added to the fracturing fluid in sufficient amount tobring the concentration of the sodium molybdate to 50 ppm by weight offracturing fluid.

While the disclosure has been described with respect to a limited numberof embodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope of the invention as disclosed herein.Accordingly, the scope of the invention should be limited only by theattached claims.

What is claimed is:
 1. A method of controlling sulfides in asubterranean formation, comprising: injecting a fluid comprising aninorganic nitrate and a friction reducer into the subterraneanformation; and allowing the inorganic nitrate to increase the growthrate of nitrogen-reducing bacteria in the formation so as to inhibit thegrowth rate of sulfate-reducing bacteria in the formation.
 2. The methodof claim 1 wherein the inorganic nitrate is selected from the groupconsisting of potassium nitrate, sodium nitrate, ammonium nitrate, andmixtures thereof.
 3. The method of claim 1 further comprising: injectingnitrogen reducing bacteria into the subterranean formation.
 4. Themethod of claim 1 wherein the nitrogen reducing bacteria is selectedfrom the group consisting of Campylobacter sp. Nitrobacter sp.,Nitrosomonas sp., Thiomicrospira sp., Sulfurospirillum sp., Thauera sp.,Paracoccus sp., Pseudomonas sp., Rhodobacter sp., Desulfovibrio sp., andmixtures thereof.
 5. The method of claim 4 wherein nitrogen reducingbacteria is Nitrobacter vulgaris, Nitrosomonas europea, Pseudomonasstutzeri, Pseudomonas aeruginosa, Paracoccus denitrificans,Sulfurospirillum deleyianum, and Rhodobacter sphaeroides.
 6. The methodof claim 1 further comprising: injecting a molybdate or molybdate saltinto the subterranean formation.
 7. The method of claim 6 wherein themolybdate salt is selected from the group consisting of sodiummolybdate, lithium molybdate, and mixtures thereof.
 8. The method ofclaim 1 further comprising: injecting 9, 10-anthraquinone into thesubterranean formation.
 9. The method of claim 1 wherein no effectiveamount of a biocide is introduced into the subterranean formation. 10.The method of claim 1 wherein the subterranean formation comprises a lowpermeability subterranean formation.
 11. The method of claim 1 whereinthe fluid further comprises a brine.
 12. The method of claim 1 whereinthe fluid further comprises a scale inhibitor.
 13. The method of claim 1wherein the fluid further comprises a molybdate or molybdate salt. 14.The method of claim 1 wherein the fluid further comprises 9,10-anthraquinone.
 15. A method of controlling sulfides in a subterraneanformation, comprising: injecting a fluid comprising an inorganic nitrateinto the subterranean formation, wherein the fluid comprises a gel; andallowing the inorganic nitrate to increase the growth rate ofnitrogen-reducing bacteria in the formation so as to inhibit the growthrate of sulfate-reducing bacteria in the formation.
 16. The method ofclaim 15 wherein the fluid does not comprise an effective amount of abiocide.
 17. The method of claim 15 wherein the fluid further comprisesa molybdate or molybdate salt.
 18. The method of claim 15 wherein thefluid further comprises 9, 10-anthraquinone.
 19. The method of claim 15wherein the fluid further comprises a scale inhibitor.
 20. The method ofclaim 15 wherein the fluid further comprises a brine.